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The amidine complexes cis-[L(2)PtNH==C(R){1-MeCy(-2H)}]NO(3) (R = Me, 1a; Ph, 1b, Me(3)C, 1c; Ph(2)(H)C, 1d) and cis-[L(2)PtNH==C(R){9-MeAd(-2H)}]NO(3) (R = Me, 2a; Ph, 2b; Me(3)C, 2c; Ph(2)(H)C, 2d), are formed when cis-[L(2)Pt(μ-OH)](2)(NO(3))(2) (L = PPh(3)) reacts with 1-methylcytosine (1-MeCy) and 9-methyladenine (9-MeAd) in solution of MeCN, PhCN, Me(3)CCN and Ph(2)(H)CCN. Reaction of 1a,b and 2a,b with HCl affords the protonated amidines [NH(2)==C(R){1-MeCy(-H)}]NO(3) (R = Me, 3a; Ph, 3b) and [NH(2)==C(R){9-MeAd(-H)}]NO(3) (R = Me, 4a; Ph, 4b) and cis-(PPh(3))(2)PtCl(2) in quantitative yield. Treatment of 3b and 4b with NaOH allows the isolation of the neutral benzimidamides NH(2)-C(Ph){1-MeCy(-2H)} (5b) and NH(2)-C(Ph){9-MeAd(-2H)} (6b). In the solid state 3b shows a planar structure with the hydrogen atom on N(4) cytosine position involved in a strong H-bond with the NO(3)(-) ion. Intermolecular H-bonds between the oxygen of the cytosine ring and one of the H atoms of the amidine-NH(2) group allow the dimerization of the molecule. A detailed analysis of the spectra of 3b in DMF-d(7) at -55 °C indicates the presence of an equilibrium between the species [NH(2)==C(R){1-MeCy(-H)}]NO(3) and [NH(2)==C(R){1-MeCy(-H)}](2)(NO(3))(2), exchanging with trace amounts of water at 25 °C. [(15)N,(1)H]-HMBC experiments for 5b and 6b indicate that the amino tautomer H(2)N-C(Ph){nucleobase(-2H)}, is the only detectable in solution and such structure has been confirmed in the solid state. The reaction of 5b and 6b with cis-L(2)Pt(ONO(2))(2) (L = PPh(3)), in chlorinated solvents, determines the immediate appearance of a pale yellow colour due to the coordination of the neutral amidine, likely in its imino form HN==C(Ph){nucleobase(-H)}, to give the adducts cis-[L(2)PtNH==C(Ph){nucleobase(-H)}](2+). In fact, addition of "proton sponge" leads to the immediate deprotonation of the amidine ligand with formation of the starting complexes 1b and 2b.

Metal-promoted synthesis of amidines containing the model nucleobases 1-methylcytosine and 9-methyladenine